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EPSRC Reference: GR/K17484/01
Title: ASYMMETRIC CARBON-CARBON BOND FORMATION USING LIGAND ACCELERATED CATALYSIS
Principal Investigator: Berrisford, Dr D
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Department: Chemistry
Organisation: UMIST
Scheme: Standard Research (Pre-FEC)
Starts: 28 February 1996 Ends: 27 February 1999 Value (£): 6,320
EPSRC Research Topic Classifications:
Asymmetric Chemistry
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Summary on Grant Application Form
One of the most interesting innovations in the field of metal mediated asymmetric synthesis is the emergence of processes which exhibit ligand accelerated catalysis. In its most useful embodiment, the ligand should be chiral and able to induce asymmetry during a bond forming process. The initial chemistry of interest will be the reactions of allyl or crotyltrichlorosilanes with aldehydes to give homoallylic alcohols with control of enantio-and diastereoselectivity. It has been shown that a ligand such as an achiral phosphoramide promotes transfer of the allyl or crotyl group while there is no observable reaction in the absence of the ligand. Maximum priority will be given to the synthesis of novel C3-symmetric chiral phosphoramides, ligand class which has been rarely studied. Despite a wealth of study on asymmetric catalysis, little attention has been directed at neutral oxygen ligands which have a high donor capacity. Moreover, this ligand type seem to be prime candidates when seeking to exploit the chemistry of hypervalent silicon in asymmetric catalysis. The discovery of additional reaction types which might be amenable to promotion using O-donor ligands for silicon is a major impetus for this project. It is proposed that the chemistry benefits from its simplicity and its catalytic nature, both virtues in contemplating commercial application.
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